Indamines process for producing the same and compositions containing indamines and processes for dyeing keratinous fibers using said compositions

ABSTRACT

INDAMINE HAVING THE FORMULA   1-R1,2-(R2-NH-),3-((2-R4,3-R5,4-NH2,5-R6,6-R7-PHENYL)-N=),   5-R3,6-(NH=)CYCLOHEXA-1,4-DIENE   WHEREIN R1, R3, R4, R5, R6 AND R7 EACH REPRESENT HYDROGEN, A LOWER ALKYL OR LOWER ALKOXY AND R2 REPRESENTS HYDROGEN OR A LOWER ACYL, AND THEIR ACID ADDITION SALTS AND THEIR DOUBLE ZINC SALTS ARE USEFULLY EMPLOYED FOR DYEING KERATINOUS FIBERS AND, IN PARTICULAR, HUMAN HAIR. THE INDAMINES CAN BE IN A TAUTOMERIC FORM OF THAT REPRESENTED ABOVE.

United States Patent O M US. Cl. 8-101 10 Claims ABSTRACT OF THEDISCLOSURE Indamine having the formula wherein R R R R R and R eachrepresent hydrogen, a lower alkyl or lower alkoxy and R representshydrogen or a lower acyl, and their acid addition salts and their doublezinc salts are usefully employed for dyeing keratinous fibers and, inparticular, human hair. The indamines can be in a tautomeric form ofthat represented above.

The present invention relates to novel indamines having formula:

wherein R R R R R and R each independently represent a member selectedfrom the group consisting of hydrogen, lower alkyl having 1-6 carbonatoms and lower alkoxy having 1-6 carbon atoms and R represents a memberselected from the group consisting of hydrogen and lower acyl having l6carbon atoms and to the salts vformed by these indamines with organic orinorganic acids, in particular, their acetates, hydrochlorides,persulfates, perchlorates and the double zinc salts of these compounds,which can, of course, be in a tautomeric form of that represented byformula (I).

Generally, the indamines of formula (I) are isolated in the form oftheir salts, these latter generally being more easy to obtain because ofsolubility.

The indamines or indamine salts of formula (I) can be prepared bycondensing a compound having the formula NHz

NH R:

wherein R R R have the meaning given above on a paraphenylenediaminehaving the formula HzN- NH:

Rs B1 where R R R R also have the meaning given above.

The condensation reaction can be carried out in an alkaline aqueous oraqueous-acetonic medium in the presence of an oxidizing agent. Theinitial reactants, represented by formulae II and III above can be usedin the form of one of their salts. If necessary or desirable, theresulting indamine or indamine salt can be further transformed into thedesired indamine salt.

The oxidizing agent used in the above condensation reaction isadvantageously hydrogen peroxide, a peroxy salt and, in particular, analkaline persulfate or ammonium persulfate, the use of the latterfacilitating the isolation of the indamine of formula I in the form ofan insoluble persulfate.

When the oxidizing agent used is hydrogen peroxide and it is desired toobtain an indamine salt that is relatively insoluble in Water, the abovecondensation can be followed by addition to the reaction mixture eitherof an acid corresponding to the desired salt, or of a salt of that acidwhich is more soluble in water than the desired indamine salt, forexample, ammonium persulfate.

It has further been noted that even when it is desired to prepare anindamine persulfate, it is often advantageous to proceed in two stages,the first stage comprising carrying out the condensation in the presenceof hydrogen peroxide and the second stage comprising adding ammoniumpersulfate or an alkaline persulfate to the reaction mixture.

When it is desired to obtain indamine salts which are very soluble inwater, it is necessary to produce these salts in a two stage operation.In the first stage, there is prepared an indamine salt such as apersulfate or a hydrochloride which is relatively insoluble and,therefore, can be isolated. In the second stage, this salt is heatedwith an alkaline solution from which the indamine of formula I can beextracted with a suitable solvent. This indamine can then be changedinto the desired salt by the addition of the corresponding acid to thesolvent phase. This way of operating is particularly applicable when itis desired to prepare an acetate of the indamine.

When it is desired to obtain an indamine of formula (I), which is notsalified and which is insoluble in water, the condensation reaction ispreferably performed in the presence of hydrogen peroxide and theresulting indamine is separated from the reaction medium by any suitabletechnique, for example, by filtering.

On the other hand, when it is desired to obtain an indamine of formula(I) which is so soluble in water that its direct isolation from thereaction medium is not feasible, the indamine, after being prepared bythe above condensation reaction in the presence of hydrogen peroxide, isconverted, in a first stage, into a water insoluble salt thereof such asits persulfate or its hydrochloride, by operating in the way describedabove. The salt thus formed is isolated as by filtering, for instance,and then in a second stage is treated with a concentrated alkalinesolution, operating in a minimum of water. Finally, if necessary ordesirable, the indamine is extracted with a suitable solvent such aschloroform or methylisobutylketone.

To obtain double salts of zinc and the indamine of formula (I), itsufiices to add an aqueous solution of a suitablle zinc salt to anaqueous solution of soluble indamine sa ts.

Representative paraphenylenediamines that can be used in accordance withthe present invention are, for example, paraphenylenediamine,paratoluylenediamine, 2,5-diaminoanisole, 2,5 diaminochlorobenzene, 2methoxy-S- methyl paraphenylenediamine, 2,6 dimethyl-S-methoxyparaphenylenediamine and 1,4-diaminodurene.

Compounds representative of those having formula II above include, forinstance, 2,4-diaminoanisole, 2,4-diaminobenzene, 3-amino-4-methylacetanilide and meta amino acetanilide.

The condensation reaction is generally carried out at atmosphericpressure and at a temperature ranging from about 10 C. to 30 C.Generally, the paraphenylene diamine and the compound represented byformula II are employed in essentially equimolar amounts. When thereaction medium is an alkaline aqueous acetonic solution, acetone cancomprise between about 10 to 30 weight percent of the medium. Thealkalinizing agent, which can be ammonia or an organic amine, such asmonoethanolamine, is present in amounts such that the pH is about 8 to10. The oxidizing agent is generally present in amounts at least equalto the theoretical amount necessary for making the desired quinonediimine.

Further, it is possible to prepare the indamines of formula (I) whereinat least two of the radicals R R R and R are other than hydrogen and thesalts of these indamines, by condensing a compound having the formula(II) on a benzoquinonediimine having the formula NH- =NH a B1 (IV)wherein R R R R, have the meaning indicated above with the proviso,however, that at least two of these radicals are other than hydrogen.The condensation is carried out either in an aqueous medium, or in aninert organic solvent such as methylisobutylketone, dioxane or benzene.Optionally, there can be present in the reaction medium, when anindamine salt is desired, an acid corresponding to this desired salt.

When the condensation is performed in water, it is possible, by additionto the reaction mixture of a salt such as sodium chloride, ammoniumpersulfate and sodium perchlorate, to isolate the resulting indamine inthe form of a relatively water-insoluble salt.

When it is desired to prepare indamine salts that are very soluble inwater, the condensation reaction is preferably performed in an organicsolvent such as methyl isobutyl ketone or the like. Then the acidcorresponding to the desired salt, for example, acetic acid or propionicacid, is added to the solvent.

Generally, in this embodiment of the present invention the benzoquinonediimine and the compound represented by formula H are also used inessentially equimolar amounts and the condensation reaction is carriedout usually at atmospheric pressure and at a temperature ranging fromabout 10 C. to 25 C.

The indamines according to the present invention, and their salts,constitute dyes which have a great dyeing power in a broad pH range,which can range from pH to pH 10. Because of their great aflinity forkeratinous fibers, very slight concentrations of these dyes aresufficient to obtain intense shades, which explains why those saltsthereof which are relatively insoluble in water, such as the persulfatesand certain chlorides, are perfectly usable.

Consequently, the present invention also provides novel dyeingcomposition for keratinous fibers, in particular, for human hair,characterized by the fact that it contains in solution at least onecompound represented by formula I or a salt of this compound.

The dye compositions according to the invention can contain only thecompounds of formula I, in which case they make it possible to obtain onwhite hair tints which go from violet blue to green, after an extremelyshort application period, of the order of three minutes at ambienttemperature.

Because of the great dyeing power of the novel compounds of formula (1)their concentration in the compositions according to the invention can,as said above, be extremely slight, of the order of 0.002% by weight.However, this concentration can vary from about 0.002 to 1% by weight.

The compositions according to the invention can also contain otherdirect dyes, for example, anthraquinone dyes, nitro dyes of the benzeneseries, indoanilines, indophenols or indamines other than those offormula (I).

The compositions according to the invention make it possible to obtainshades richin glints which often give the hair a pearly appearance.

The dye compositions according to the invention are generally in theform of aqueous or aqueous alcohol solutions which can easily beprepared by dissolving in water one or more compounds of formula I inmixture or not with other direct dyes. However, they can also containthickeners and be in the form of creams or gels. When an alcoholsolution is employed generally, the alcohol will be a lower alkanol suchas ethanol or isopropanol, the alkanol being present in the aqueoussolution in amounts of about 20 to 70 percent by weight thereof.

The compositions according to the invention can further contain variousingredients usually used in cosmetics, for example, wetting agents,dispersing agents, swelling agents, penetrating agents, softeners orperfumes. They can also be packaged under pressure in aerosol bombs orcontainers, together with a conventional aerosol propellant such adichlorodifluoromethane, trichloromonofluoromethane and their mixtures.Obviously, other conventional aerosol propellants can also be used.

The pH of the dye compositions according to the invention can varybetween 4 and 10. Preferably, however, the pH ranges between about 6-9.

Dyeing of keratinous fibers, in particular human hair, with dyecompositions according to the invention, can be performed in the usualway by application of the composition to the fibers to be dyed, thecomposition being left in contact with the fibers for a time varyingfrom about 3 to 30 minutes. Following this application, the fibers arerinsed and, if desired, washed. Thereafter, the thus treated fibers aredried.

In another embodiment of the present invention, the novel indamines canbe employed in the production of capillary hair-setting lotions. Theselotions comprise an aqueous alcohol solution, at least one cosmeticresin and at least one indamine of formula I or a salt thereof. Theamount of indamine present in the hair-setting lotion of the presentinvention can be extremely low. Such an amount generally ranges betweenabout 0.002 to 0.5% by weight of the total hair-setting lotioncomposition.

Representative cosmetic resins that can be employed in the hair-settinglotion composition of the present invention include, for instance,polyvinyl-pyrrolidone having a molecular weight ranging from about10,000- 70,000, copolymer of crotonic acid and vinyl acetate, copolymerof vinylpyrrolidone and vinyl acetate wherein the ratio of PVP to PVAranges between 50-70250-30, copolymer of maleic anhydride and butylvinylether and the like. These resins are utilized in a proportion of about 1to 3% by Weight.

The alcohols suitable for the preparation of the hairsetting lotions ofthe invention are low molecular weight alkanols, preferably ethanol orisopropanol which are present in amounts of about 20% to 50% by weightof the total hair-setting lotion composition. The pH of the hair-settinglotion of the invention can range from about 4-10 and preferably betweenabout 6-8.

Hair-setting lotions of the present invention that contain onlyindamines of the present invention are shading or tinting compositionswhich make it possible to impart to the hair extremely luminous glintsand often to give them a pearly or iridescent appearance.

However, the hair-setting lotions of this invention can also containother direct dyes, for example, anthraquinone dyes, nitro dyes of thebenzene series, indoanilines, indophenols or again other indamines.These lotions are used in the customary way by applying the same to wethuman hair which has been previously washed and rinsed, followed byrolling up and drying of the air.

The following examplesare intended to illustrate the various aspects ofthe present invention. Unless otherwise specified, all parts andpercentages are by weight and all temperatures are expressed in degreescentigrade.

EXAMPLE 1 2 H NQ-NQNH-CEC 0111-1320 on. cm

0.04 mole (6 g.) of 2-methyl-5-methoxy benzoquinone diimine is dissolvedin 160 cc. of methylisobutyl ketone. There is then immediately added tothis solution 0.04 mole (5.52 g.) of 2,4-diaminoanisole in 120 cc. ofmethylisobutylketone to which are added 4.4 cc. of acetic acid. Theresulting above indamine precipitates and is filtered from the reactionmedium. Thereafter, the precipitate is washed with a little acetone anddried. 4.30 g. of chromatographically pure indamine acetate,crystallized in monohydrate form and melting at 135 C. are thusrecovered.

Molecular mass calculated for C H N O -H O: 364.

Molecular mass found by potentiometric measurement by perchloric acid inacetic acid: 357.

Calculated for- Analysis OirHuNtOt-HtO Found Percent:

EXAMPLE 2 The semihydrate of the acetate of N-[(4'-amino-2methoxy-5'-methyl)phenyl]-3 amino 6 methyl benzoquinone diimine isprepared as follows:

CH2 NH:

HzN N- .NH- CHaC OzH-0.5 H2O Calculated for- Analysis CnHnOrNrOjHzOFound Percent:

EXAMPLE'3 v The hydrochloride of N-[ (4'-amino-2 methoxymethyl)phenyl]-3-amino-6 methyl benzoquinonediimine is prepared asfollows:

0.01 mole (3.39 g.) of indamine acetate, prepared as in Example 2, isdissolved in 10 cc. of ice water to which are added 3 cc. of ammonia at22 Be. This solution is saturated with sodium chloride and after 20minutes of cooling at 0, the aboveindamine is filtered from theraectionmediuni inthe form of beautiful green crystals.

.25 g. of this desired indamine hydrochloride which ischromatographically we ar thus mastered.

EXAMPLE 4 N-[(4'-amino 2' methoxy 5' methyl)phenyl] 3- amino 6 methylbenzoquinoneimine is prepared as follows: v

0.01 mole (3.39 g.) of indamine acetate, prepared as in Example 2, isdissolved in 10 cc. of ice water to which have been added 3 cc. ofammonia at 22B. The ammonia solution is'immediately extracted withchloroform. The chloroform phase is washed withwater and petroleum etheris added thereto in a volume amount equaling the chloroform phase. Theabove indamine is then filtered therefrom inthe form of deep garnetcrystals. 1.5 g. of chromatographically pure indamine which melts at 164after drying under a vacuum are thus recovered.

Molecular mass calculated for C H ON 270.

Molecular mass found by potentiometric determination by perchloric acidin acetic acid: 278.

EXAMPLE 5 EXAMPLE 6 The acetate of N-[ (4'-amino-2'-methoxy 5' methyl)phenyl]-3-amino-2,6-dimethyl benzoquinone diimine is prepared asfollows:

OCH: NH: (E 1 HaN N- NH- CHzC 0211 Ha Ha 0.0282 mole (4.23 g.) ofZ-methyl 5-methoxy-benzoquinonediimine is dissolved in cc. ofmethylisobutylketone. There is then immediately added to this solution0.0282 mole (3.83 g.) of 1,3-dimethyl-2,4-diamino benzene (meltingpoint= 66 C.) in 60 cc. of methylisobutylketone to which are added 3.25cc. of acetic acid. 4.6 g. of chromatographically pure indamine acetateprecipitate and are immediately filtered and are dried for 8 days undervacuum. The above indamine melts at'172.

Calculated for- Analysis CIEHRAN403 F und Percent: I 1 C-.....-..'..62.77 62. 46 62.53 H 7.02 6.97 7.06 N 16. 27 16. 08 16. 12

1 Molecular mass calculated for C H N O 344. I

Molecular-mass found by potentiometric determination byperchloric'acidinacetic acid: 348. H

Y EXAMPLEIT vThe acetate ofN-[(4'-aminow2'-methoxy-3',5'-dimethyl)phenyl]-3-amino-2,6-dimethylbenzoquinone diimine is prepared as follows:

0.037 mole (0.606 g.) of-2,6 dimethyl-3-methoxy benzoquinonediimine isdissolved in 15 cc. of methylisobutylketone. To this solution there isimmediately added 0.037 mole of 1,3-dimethyl-2,6-diamino benzene insolution in 12 cc. of methylisobutylketone to which has been added 04cc.acetic acid. 0.37 g. .of indamine acetate precipitates in crystallineform and is filtered from the reaction medium. The resulting inamine iswashedwith a little methylisobutylketone and dried under vacuum.' It ischromatographically pure and melts at 164.

Molecularmass calculated forv C H O N 358.

Molecularmass .found by poteniometric determination by perchloric acid.in acetic acid: 355

Calculated for- Analysis CltHreOaNt Found Percent:

C 63. 68 63. 40 63. 52 H 7. 26 7. 32 7. 24 N 15. 64 15. 50 15. 48

EXAMPLE 8 p The persulfate of N-[(4'amino-2'-methoxy-3,5'dimethyl)phenyl]-3-acetylamino6-methyl benzoquinonediimine is preparedas follows: f

To a solution of 0.03 mole '(7.17 g.) of the dihydrochloride of2,6-dimethyl-3-methoxy paraphenylenediamine in 20 cc. of water to whichare added 20cc. of ammonia at 22 B. there are added, on the one hand,0.03 mole (4.92 g.) of 3-amino-4-methyl acetanilide in solution in 40cc. of acetone and, on the other hand, 50 cc. of 50 volume hydrogenperoxide. The reaction mixture is left at ambient temperature for 15minutes and cooled to Acetic acid in amounts sufficient to obtain a pHof 8 is added thereto. Then a saturated aqueous solution of ammoniumpersulfate is added. The desired indamine persulfate immediatelyprecipitates in the form of beautiful green crystals with golden glints.The crystals are filtered, washed with a little water and then withacetone. After drying under vacuum, 4.86 g. of chromatographically pureindamine persulfate are obtained.

EXAMPLE 9 The acetate of N-[(4'-amino-2-methoxy-3',5-dimethyl)phenyl]-3-acetylamino-6-rnethyl benzoquinone diimine is prepared asfollows:

CH: OCH: IIIHCOCHI Hm N==NH- omc 0211 H: CH8

2 g. of indamine persulfate, prepared according to Example 8, areintroduced with stirring into 40 cc. of an iced 0.2 N sodium hydroxidesolution. The indamine,

released with methylisobutylketone, is immediately ex-v Calculated forAnalysis C zoHztNaOa Found Percent:

C 62. 16 62. 16 62. 10 H 6. 78 6. 68 6. 60 N 14. 50 14. 55 14. 30

en. eon: NHQQCH:

Hm -N =NH Hero.

0.01- mole (1.865 g.) of metaaminoacetanilide-hydrochloride is dissolvedin 6 cc. of water. 1 cc. of ammonia at 22 B. is added to this solution.Then there is added a solution, prepared .at the moment of use, of 0.01mole (1.64 g.) of 2,6-dimethyl-3-methoxy benzoquinone diimine in 6 cc.of ice water. The reaction mixture instantly takes on an intense greencoloring. A solution of 1.6 g. of sodium perchlorate in 3 cc. of wateris. added. The above indamine precipitates and is filtered from thereaction medium after which it is washed with a little water and dried.2.5. g. of the desire inamine perchlorate, which is .chromatographicallypure are thus recovered.

EXAMPLE 11 The following hair-settingslotion composition is prepared:

G. Dye of Example 1 0.02 Vinyl acetate-crotonic acid copolymer 'vinylacetate, 10% crotonic acid-molecular weight, 45,000 to 50,000) 2Ethanol-96 titer, q.s.q., 50. Water, q.s.q. 100

Triethanolamine, I q.s.q., pH 7.

This hair-setting lotion when applied to bleached hair imparts thereto aclear silvery blue shade.

.. EXAMPLE 12 The following dye composition is prepared:

G. Dye of Example 1 0.005 Water, q.s.q. 100

Ammonia at 22 B., q.s.q., pH 10.

This composition when applied to bleached hair for three minutes,imparts thereto after rinsing and shampooing, a very clear pearly blueshade.

EXAMPLE 13 The following hair-setting lotion composition is prepared:

Triet-hanolamine, q.s.q. pH 7.

This hair-setting lotion when applied to brown hair imparts theretoclear parma shade.

7 EXAMPLE 14 The following hair-lotion composition is prepared:

. G. Dye of Example 1 0.2 Vinyl-acetate-crotonic acid copolymer (vinylacetate, 90%, crotonic acid, 10%molecular weight 45,000) 2 Ethyl alcohol96 titer, q.s.q., 50". Water, q.s.q. 100

Triethannolamine, q.s.q., pH 7.

9. EXAMPLE 15 I I ,The following dye composition is prepared;

Dye of Example 1 0.02 Nitro-orthophenylene diamine L 0.1 Ethyl alcohol,96 titer 20 Water, q.s.p. 100

Ammonia, 22 B., q.s.p., pH 10. I II I I This dye composition whenapplied to 95% naturally white hair for 20 minutes imparts thereto agreen shade, after using and shampooing. I

1' EXAMPLE 16 The following hair-setting lotion is prepared;

Dye'of Example 2 .'j 0.05 Vinyl'acetate-crotonic acid copolymer (vinylacetate,

90%, crotonic acid, l%- -molecular weight 45,000) 2' 20 Isopropylalcohol, 96% titer,q.s.p., 50 Water, q.s.p. 100

Triethanolamine, q.s.p., pH 7.

This hair-setting lotion when applied to bleachedhair imparts thereto ablue shade with pearly glints.

I, EXA PLEQ17 The following hair-setting lotion is'prepared;

Triethanolamine, q.s.p., p H II I II I I This hair-setting lotion whenapplied to bleached hair imparts thereto a gray blue shade.

EXAMPLE 1 s The "following dye composition is prepared:

Dye of Example 3 0.15 Water, q.s.p. 100

Ammonia at 22 B q.s.p., pH 8. I I

- This dye composition when applied to 95% naturally white hair for10minutes, after rinsing and shampooing, imparts thereto a deep bluecoloring.

E AMPL .19"

The following hair setting lotion composition is prepared:

Dye of Example 5 0.1

Vinyl acetate-crotonic acid copolymer (vinyl acetate, 90%, crotonicacid, %-.molecular weight 45,000) 2 Ethyl alcohol, 96 titer, q.s.p., 50.

Water, q.s.p. 100

Triethanolamine, q.s.p., pH 7. Q

This hair settinglotion when applied to bleached hair imparts thereto ablue shade. A

EXAMPLE The followingdye composition is prepared:

Dye of Example 6 0.2 .Butylglycolq M, ,g I, 5

Lauryl alcohol oxyethylenated with 10.5 moles'of ethylene oxide H ;5Water, q.s.p. v. 1

This dye composition when applied to 60% naturally white hair for 20minutes, after rinsing and shampooing imparts thereto a deep Prussianblue coloring.

EXAMPLE 21 The following hair-setting lotion composition is prepared:

G. Dye of Example '6 0.05 N-[(4' hydroxy)phenyl]-3-amino-6-methylbenzoquinoneimine 0.2 Vinyl acetate-crotonic acid copolymer (vinylacetate, crotonic acid, 10%molecular weight 45,000) Ethyl alcohol, 96titer, q.s.p., 50. Water, q.s.p. 100

Triethanolamine, q.s.p., pH 7. a

This hair-setting lotion when applied to bleached hair imparts thereto aclear bronze shade.

EXAMPLE 22 The following dye composition is prepared:

- G. Dye of Example 7 0.02 Water, q.s.p.. 100

Ammonia, at 22 B., q.s.p., pH 7.

This dye composition when applied to naturally white hair for 20minutes, after rinsing and shampooing, imparts thereto a very luminousblue shade with silvery glints.

EXAMPLE 23 The following dye composition is prepared:

' G. Dye of Example 7 0.02 N-[(2,4-diamino 5' methoxy)phenyl]benzoquinone 0.2 Water, q.s.p.

This dye composition when applied to 95 naturally white hair for 20minutes, after rinsing and shampooing, imparts thereto a violet shadewith iridescent glints.

I EXAMPLE 24 The following hair setting lotion composition is prepared:

G. Dye of Example 8 0.1 Vinyl acetate-crotonic acid copolymer (vinylacetate, 90%, crotonic acid, 10%-molecular weight 45,000) 2Ethylalcohol, 96 titer, q.s.p., 50. Water, q.s.p. 100

This hair setting lotion when applied to bleached hair imparts thereto agreen shade.

EXAMPLE 25 The following hair-setting lotion composition is prepared:

G. Dye of Example 9 0.1 Vinyl acetate-crotonic acid copolymer (vinylacetate, 90%, crotonic acid, 10%--molecular weight 45,000) 2 Ethylalcohol, 96 titer, q.s.p. for 50. Water, q.s.p. 100

Triethanolamine, q.s.p., pH 7.

This hair-setting lotion when applied to bleached hair imparts thereto ablue green shade.

EXAMPLE 26 The following dye composition is prepared:

menial-in. 10

Ethyl'alcohol, 96 titer I 50 Water, q.s.p. 100

This dye composition when applied to bleached hair for 20 minutes, afterrinsing and shampooing, imparts thereto a green shade. Y

EXAMPLE 27 The following hair dye compositionis prepared:v

G. Dye of Example 6 0.2 Ethyl alcohol, 96 titer y*20 Water, q.s. p 1001% lactic acid sufiicient for pH 4. 1

This hair dye composition when applied to 95% naturally white hair for20 minutes, after rinsing and shampooing, imparts thereto a clearsilvery gray blue shade.

EXAMPLE 28 The following hair dye composition is prepared:

Dye of Example 4 0.05 Isopropyl alcohol, 96 titer 40 Water, q.s.p. 100

D 1 wherein R is selected from the group consisting of hydrogen andlower alkyl, R is selected from the group consisting of hydrogen andacetyl, R is selected from the group consisting of hydrogen,

lower alkyl and lower alkoxy,

R is lower alkoxy, R is selected from the group consisting of hydrogenand lower alkyl,

R is lower alkyl and R is hydrogen (b) an acid salt of said indamine in(a) and (c) a double chloride of zinc and said indamine in (a),

said compound being present in amounts of about 0.002

to 1% by weight of said composition.

2. The composition of claim 1 having a pH between 4-10.

3. The composition of claim l'having a 6-9.

4. The composition of claim 1 wherein the aqueous solution furthercontains a lower alkanol and a film forming resin selected from thegroup-consisting of polyvinylpyrrolidone having a molecular weightranging from 10,000-70,000 and a copolymer of 10% crotonic acid and 90%vinyl acetate having a molecular weight ranging from 45,000-50,000 inamounts of about l to 3% based on the weight of said composition.

5. The composition of claim 4 wherein said lower alkanol is selectedfrom the group consisting of ethanol and isopropanol.

6. The composition of claim 4 wherein said lower alkanol is present inamounts ranging from about 20-50 percent by weight of said composition.

7. The composition of claim 4 wherein said compound is present inamounts of about 0.002 to 0.5% by weight of said composition.

pH between .{the semihy d rate of the ace ttristrm' 12 8. Thecompositionof cIaim'I'Wherein said compound is selected .from thegroupconsisting of e the monoh ydr'ateof amateur N-I (4"-aniino -'2'metlioxy- 5' methyl)phenyl]-3-amino6-methoxy..benzoquinone diirnine, i 1

v thox'y-s methyl) phenyl] 3-amino-6-methyl none diim'ine. Y thehydrochloride of N-['(4-amino-2"-methoxy-5'-rnethyl phenylj -3-amino-6methy1 ben'zoquihonqdiimine, N-[ (4' ar'nino-2 q'nethOXy-S "-methyl)phenyl-] -3-a'mino'- 6-methyl benzoquinoneimine; T; 1 i the doublechloride of zinc and N -[(4'-amino-2'-methoxy- 5'-methyl)phenyl]3-aminomethyl benzoquinone di- 1rn1ne,.-:

jj :11. the acetate of N-[(4'-amino- '-methoxy- 5'-methyl)phenyl]-3-amino2,6-dimethyl benzoquinone-sdiimine,'l the acetate ofN-[(4f-amino-2-methoxy-3, dimethyl}. phenyl] -3-amino.-2,6edimethylhenzoquinone.v diimine, the persulfate of.N-[4'-arnino-2'-methoxy-3',5':dimethyl) phenyl]-3-acetylamino-.6-methylbenzoquinone diimine,

wherein 7' R is selected from the R is selected from the groupconsisting of hydrogen and R is selected from the group'consisting'of-hydrogen,

methyl and methoxy,

R is methoxy,

R is selectedfrom-fthe'.group, consisting of hydrogen,

-- and methyl,

R is methyland R ishydrogen (b) an acid salt of said indamine in (a) andi. :1

(c) a double chloride of zinc and said. indamine in (a),

'said compound being present infamounts of about 0.002'to"l% by weighttif saidl composition. I 10. A process for"'dyeing'human'ha ir whichcomprises applying to said hair in an amount effective to dye the samean aqueous solution containing 0.002 to 1% by wfeight of'a-cor'ripoundselected fror'nthe group consisting (a) an indamine having the formulagroup consisting of hydrogen and Hmrrrm and hydrogen,

"R is hydrogen 13 (b) an acid salt of said indamine in (a) and (c) adouble chloride of zinc and said indamine in (a), said compositionremaining in contact with said hair for a period ranging from about 3 to30 minutes, rinsing and drying said hair.

249,136 11/1881 Witt 260396 N X 14 6/1914 Fischer 96-100 X OTHERREFERENCES Kass et al., Journal of the Society of Cosmetic Chem- 5 ists,April 1961, pp. 151-153.

STANLEY J. FRIEDMAN, Primary Examiner US. Cl. X.R.

